US1989042A - Nitrogenous polymerization - Google Patents

Nitrogenous polymerization Download PDF

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US1989042A
US1989042A US1989042DA US1989042A US 1989042 A US1989042 A US 1989042A US 1989042D A US1989042D A US 1989042DA US 1989042 A US1989042 A US 1989042A
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D251/00Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B6/00Anthracene dyes not provided for above

Description

Patented Jan. 22, 1935 NITROGENOUS PoLYMERr'znTron. I

PROD

Max Albert Kunz, Mannheim, and Karl Koeberle and Erich jBerthold, Ludwigshafen-on-the- Rhine, Germanm assignors to General Aniline Works, Inc., New York, N. Y., a corporation a:

Delaware No Drawing. Application December 4, 1930, Se- 5 I ,iigazlgNo. 500,136. In Germany December 11,

"6 Claims. (01. 260-27) The present invention relates to derivatives of the hypothetical trihydrocyanic acid and process of producing same.

. Wehave found that. derivatives of the,hypothetical trihydrocyanicacid;

are obtained in excellent yields in a manner readily carried out industrially by treating cyclic cyanogen compounds, especially; aromatic carbocyclic and heterocyclic cyanogen compoundswith inorganic acid condensing agents practically free from water, whereby, when treating mononuclear cyclic cyanogen compounds, halides must be present. -Acid condensing agents of the, aforesaid kind are," for example, sulphuric acid,; oleum, chlorosulphonic acid, phosphoric acid, hydro fi halides, aluminium chloride, zinc chloride and phosgene. When polymerizing mononuclear cyanogemcompounds the presence of halides may be ensured by employing such of the beforementioned condensing agents as are themselves halides, such. as f or'example chlorosulphonic acid, or mixtures of the said condensing agents comprising such halides, or by adding other-halides, such as alkali metal or, alkaline earth metal halides, to the beforementio'ned condensing acids. The polymerization may'also be carried out in the presence of organic solvents or diluents, the presence of such diluents' being advantageous when eflecting polymerization by means of acid chlorides. Organic diluents'which may be used are for example benz'ene and its homologues, halogenbenzenes, nitrobenzenes, pyridine and glacial acetic acid. The polymerization takes 'placefalready at ordinary temperatures with evolution'of heat. With cyclic cyanogen compounds of the benzene and naphthalene series polymerization occurs so violently that it'is advantageous to cool the reaction imixture, whereas with cyanogen compounds of the anthraquinone seriesthe reac tion mixture may be warmed slightly. Thus for example when para-tolunitrile is intrdou'ced into chlorsulpliomc acid, pure 2,4,6 -tri-'para -tolyl- 1,3,5-triazine is obtained in very good yields within a few minutes. When a mixture is homolo gous nitriles isemployed, mixed 2,4,6'-triarylor arylalkyl -1,3,5-triazines areobtained j The polymerization products usually obtained in good yields may'bepurified by the usual methods it'necessary. ';Th'ey'a're generally speaking soluble with great difiiculty-in'organic solvents but with comparative ease in concentrated sulphuric I' V. I F: NIV The reaction products obtainable according to the present invention are partly already dyestufis and partly valuable intermediate productstfor I) the preparation'of'dyestufis. ,7 employed forpharmaceutical purposes, as

They may also be vul-i canization accelerators and the like.

The polymerization products of cyanogen compounds of the anthraquinone series and other cyanogen compounds capable of .beingivattedib'ut which need have no aflinity for the 'fibres,zusually constitute valuable vatdyestuffs giving powerful dyeings. n a i Thefollowing examples will further illustrate the nature of .this invention, but theinvention is not restricted to these examples. The partsare. by weight... i

Example 1 I 2 parts of benzoni trile. are,.introduced while stirring into 20 parts of chlorsulphonic acid cooled to 5 below'zerojcentigrade, stirring is continued for a short time at from 0 "to 10 centigrade, the temperature is allowed to rise to room temperature, stirring iscontinued for some time and the reaction mixture is poured onto ice and the 2,4,6-triphenyl- 1,3,5-triazine (cyanphenine) which separates in the 'form of a white flocculent precipitate is filtered off ,by suctiom, The yield is practically theoreticalJj The" crudeproduct which corresponds to'the'formula: j

' 1 part of 'para-tolunitrile is introducedalitt-le as at a time into 10 parts of chlorsulphonic acid cooled to 10 below zero centigrade, the whole is kept at the same temperature for half an hour, allowed towarm up slowly to room temperature, diluted. with .5 parts of concentrated sulphuric acid, poured into ice-water, filtered by suction, and the filter cake washed until neutral and dried. The crude 2,4,6-tri-para-tolyl-1,3,5triazine which corresponds to the formula:-

, H] obtained in a yield of about colourless powder .which melts at from-274 to 276 C. It crystallizes from glacial acetic acid,

toluene, xylene and nitrobenzene, in which itis.

v N v v CHa 339 M3 obtained in verygoodyields in the form of a colourless powder, melts at'from 1,515 to 148 C; Colourless needles melting at from 152 to 153 C. may be obtained therefrom by crystallization from glacialaceticacid.

' Example 4 2 200 parts of chlorsulphonic acid are cooled to 10 below zero centigrade while stirring, 6 parts of para-tolunitrile and10.3 parts of benzonitrile are slowly introduced, the whole is warmed to from 20 to 30- C., kept at this temperature for a short time and worked up in the usual manner. The resulting polymerization product is a colourless powder which melts at from 176 to 178 C. Colourless needles maybe obtained therefrom by crystallization, for example fromglacial acetic acid,

Ezample'5 2;parts' of benzonitrile are dissolvedat5 C; in 2Q ,partsof 12 per cent oleum. Dry" hydrogen bromide is led into the solution until a sample withdrawn and poured into water deposits a white flocculent precipitate. The whole is then worked'up. in the usualmanner. The reaction 'mulay percent is a product obtained is identical with that obtainable according to Example 1.

Example 6 about zero centigrade and the whole is kept at from 10 to 20. C. for several hours while stirring. The mixture is then diluted with anhydr'ous sulphuric acid, poured into ice-Water and Vfiltered' by suction. The reaction product obtained which probably corresponds to the foris a colourless powder which rnelts'at about 290 C. and which may be obtained 'in the form of colourless needles by crystallization from organic solvents.

Under the said conditions, alpha-naphthonitrile reacts in a similar manner.

Example 7 parts of 2-amino-3-cyanoanthraquinone' are dissolved in 1250 parts of 23'per cent oleuln while stirring and the wholeis heated to from 50- to 80 C. As soon as a sa'mplewithdrawn yields orange 'dyei'ngs on cotton from an olive brown vat" the whole is allowed to cool and is worked up as described in Example 6. The polymerization product obtained which'p'robably corresponds to the formula:

is an orangepowder which dissolves in concentrated sulphuric acid giving an orange colouration; and which is practically insoluble inalmost all" organic solvents. It maybe purified, when necessary, by dissolution in'sulphuric acid and dilution of the solution with water or dilute sulphuric acid by way of :the oxonium sulphate which separates as a crystalline precipitate.

The same polymerization product is obtained by treating 2-amino 3 -cyanoanthraquinone with hydrochloric acid, acid chlorides, as for example phosgene,-it being preferable to work in the presence of" diluents and at higher temperatures.

What we claim is:-

1. A- process for the manufacture of nitrogenous polymerization products-which are probably triazine, derivatives, which comprises tr'eating' -a nitrile of a mononuclear carbocyclic compound with a sulphuric acid practically free in the presence of a halide.

2. Polymerized homologues of benzonitrile which are probably triazine derivatives, the said polymerization products being difiicultly soluble in organic solvents and readily soluble in concentrated sulphuric acid.

3. Polymerized methyl derivatives of benzonitrile which are probably triazine derivatives, the said polymerization products being diflicultly soluble in organic solvents from which they crystallize in colourless needles, but readily soluble in concentrated sulphuric acid.

4. A process for the manufacture of nitrogenous polymerization products which are probably triazine derivatives, which comprises treating a nitrile of a carbocyclic compound with an ini'rom water organic acid condensing agent practically free from water and comprising a halide.

5. A process for the manufacture of nitrogenous polymerization products which are probably triazine derivatives, which comprises treating a nitrile of a carbocyclic polynuclear compound with a halogen containing inorganic acid condensing agent practically free from water.

6. A process for the manufacture of nitrogenous polymerization products which are probably triazine derivatives, which comprises treating a nitrile of a carbocyclic polynuclear compound with chlorosulfonic acid.

MAX ALBERT KUNZ. KARL KOEBERLE. ERICH BERTHOLD.

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2491459A (en) * 1949-12-13 Production of cyanuric chloride
US2503999A (en) * 1950-04-11 High-pressure synthesis of
US2525714A (en) * 1950-10-10 Preparation of z
US2559835A (en) * 1951-07-10 Reaction products of nitriles
US2598811A (en) * 1952-06-03 Of aigomattc
US2615887A (en) * 1952-10-28 Reaction products of nitriles
US2953563A (en) * 1960-09-20 Substituted s-triazine preparation
DE1137028B (en) * 1957-10-18 1962-09-27 American Cyanamyd Company A process for the preparation of trisubstituted s-triazines
US3060179A (en) * 1962-10-23 Polymerization of aromatic nitriles
US3071586A (en) * 1963-01-01 Preparation of triaryltriazines
US3238138A (en) * 1961-12-28 1966-03-01 Union Oil Co 2, 4, 6-triaryl-1, 3, 5-triazines in ultraviolet light absorption method and coatingcomposition
US3257399A (en) * 1966-06-21 Preparation of cyanuric chloride
US3264293A (en) * 1962-06-08 1966-08-02 Degussa Unsymmetrically substituted 1, 3, 5-triazines and their production

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2491459A (en) * 1949-12-13 Production of cyanuric chloride
US2503999A (en) * 1950-04-11 High-pressure synthesis of
US2525714A (en) * 1950-10-10 Preparation of z
US2559835A (en) * 1951-07-10 Reaction products of nitriles
US2598811A (en) * 1952-06-03 Of aigomattc
US2615887A (en) * 1952-10-28 Reaction products of nitriles
US2953563A (en) * 1960-09-20 Substituted s-triazine preparation
US3257399A (en) * 1966-06-21 Preparation of cyanuric chloride
US3060179A (en) * 1962-10-23 Polymerization of aromatic nitriles
US3071586A (en) * 1963-01-01 Preparation of triaryltriazines
DE1137028B (en) * 1957-10-18 1962-09-27 American Cyanamyd Company A process for the preparation of trisubstituted s-triazines
US3238138A (en) * 1961-12-28 1966-03-01 Union Oil Co 2, 4, 6-triaryl-1, 3, 5-triazines in ultraviolet light absorption method and coatingcomposition
US3264293A (en) * 1962-06-08 1966-08-02 Degussa Unsymmetrically substituted 1, 3, 5-triazines and their production

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